EP1156994B1 - Verfahren zur herstellung alkoxylierter nichtionischer tenside - Google Patents

Verfahren zur herstellung alkoxylierter nichtionischer tenside Download PDF

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Publication number
EP1156994B1
EP1156994B1 EP00910696A EP00910696A EP1156994B1 EP 1156994 B1 EP1156994 B1 EP 1156994B1 EP 00910696 A EP00910696 A EP 00910696A EP 00910696 A EP00910696 A EP 00910696A EP 1156994 B1 EP1156994 B1 EP 1156994B1
Authority
EP
European Patent Office
Prior art keywords
acid
acids
catalysts
hydrotalcite
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00910696A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1156994A1 (de
Inventor
Ansgar Behler
Horst-Dieter Schares
Almud Folge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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Filing date
Publication date
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Publication of EP1156994A1 publication Critical patent/EP1156994A1/de
Application granted granted Critical
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Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C08G65/2657—Aluminosilicates; Clays; Zeolites

Definitions

  • the invention relates to a process for the preparation of alkoxylated nonionic surfactants which one with compounds with active hydrogen atoms or carboxylic acid esters with Alkylene oxides in the presence of optionally modified hydrotalcite as a catalyst and optionally implemented other selected co-catalysts and then treated with acids.
  • nonionic surfactants are the addition products of alkylene oxides, in particular ethylene oxide and / or propylene oxide, to compounds with active hydrogen, which are usually prepared by means of homogeneous catalysis in the presence of alkali metal hydroxides or alkali metal alcoholates.
  • the homogeneously catalyzed process gives products with a broad homolog distribution. Products with a restricted homolog distribution can be obtained if the reaction is carried out in the presence of optionally modified hydrotalcites, for example in accordance with German laid -open specification DE-A-3833076 and DE-C-196 11 999 .
  • the object of the present invention was therefore to provide a method for To provide production of alkoxylated nonionic surfactants, which the Disadvantages of the complex filtration or the clouding and sedimentation of the End of reaction product no longer has.
  • the object of the present invention could be achieved if one after the alkoxylation, the catalyst hydrotalcite and any cocatalysts which may also be present not filtered off, but decomposed by adding acids.
  • the invention includes the finding that such downstream acid treatment is hydrotalcite as well as any cocatalysts that may be present are decomposed into products that are used in the Reaction mixture can remain without causing clouding or sedimentation later comes.
  • One object of the present invention therefore relates to a method for the production alkoxylated nonionic surfactants by reacting carboxylic acids with 6 to 22 carbon atoms or carboxylic acid esters with alkylene oxides in the presence of optionally modified Hydrotalcite as a catalyst and possibly co-catalysts, characterized in that after alkoxylation of acids in the form of aqueous solutions in relation to hydrotalcite and possibly Co-catalysts in molar quantities from 1: 1 to 10: 1 at temperatures between 70 and 95 ° C can be added.
  • Typical examples of this are synthetic, but preferably natural triglycerides, such as palm oil, palm kernel oil, coconut oil, rapeseed oil, olive oil, sunflower oil, cottonseed oil, Peanut oil, linseed oil, lard oil, beef tallow and lard.
  • Castor oil is preferred or hardened castor oil used.
  • fatty acid partial glycerides in particular monoglycerides of fatty acids having 12 to 18 carbon atoms, are used instead of the full esters.
  • Technical coconut fatty acid monoglycerides are particularly preferred here.
  • lower carboxylic acid esters in particular the methyl esters of carboxylic acids having 6 to 22 carbon atoms, are preferred.
  • modified hydrotalcites are used alone or in a mixture with selected cocatalysts as alkoxylation catalysts.
  • only modified hydrotalcite is used as the catalyst.
  • the modified hydrotalcites used are calcined or hydrophobized hydrotalcites, as are known, for example, from German patent applications DE-A1 38 43 713 and DE-A1 40 10 606 (Henkel). The calcined hydrotalcites are particularly preferred.
  • Modified hydrotalcites and selected co-catalysts together used as alkoxylation catalysts are suitable as co-catalysts from the group formed by hydroxides, oxides and / or alkoxides of alkali and / or Alkaline earth metals and of alkali and / or alkaline earth salts, tin salts and of Mixed metal oxides.
  • Particularly suitable hydroxides of alkali and / or alkaline earth metal hydroxides are lithium hydroxide and / or magnesium hydroxide.
  • oxides of alkali and / or alkaline earth oxides the oxides of Magnesium preferred.
  • Preferred alkoxides of the alkali and / or alkaline earth metals are those which differ from short-chain Alcohols, for example those with 1 to 8 carbon atoms and in particular derived from methanol, ethanol and / or 2-ethylhexanol.
  • the magnesium and / or barium compounds are particularly preferred.
  • alkali and / or alkaline earth salts are the magnesium and barium salts, for example the carbonates such as magnesium carbonate, or the acetates, for example Magnesium acetate of particular importance.
  • Mixed metal oxides are oxide compounds that contain at least two different metals.
  • One of the metals is preferably magnesium.
  • the other metal can be aluminum, gallium, zircon, indium, thallium, cobalt, scandium, lanthanum and / or manganese.
  • Magnesium / aluminum mixed oxides are particularly preferred.
  • the surface of the mixed oxides can be modified with one or more of the co-catalysts already mentioned, in particular with the hydroxides and / or alkoxides of the alkali and / or alkaline earth metals. Such mixed metal oxides and their modification options are described, for example, in German Offenlegungsschrift DE-A-44 46 064 .
  • Magnesium oxide is particularly preferred as co-catalyst.
  • the possibly modified hydrotalcites are sole catalysts, they are usually in amounts of 0.1 to 5, preferably in amounts of 0.5 to 1.5,% by weight on starting compounds (compounds with active hydrogen or carboxylic acid esters and alkylene oxide) are used.
  • the possibly modified hydrotalcites together with the selected co-catalysts are used, they are usually in amounts of 0.05 to 2.5 and in particular from 0.1 to 0.5% by weight, based on the starting compounds.
  • the co-catalysts can in amounts of 0.05 to 5, preferably in amounts of 0.1 to 0.5 and in particular in amounts of 0.1 to 0.3% by weight, based on the starting compounds be used.
  • hydrotalcite and the co-catalysts in the sense of the present invention even possible with a total amount of hydrotalcite and co-catalysts below 0.5 % By weight, preferably in amounts between 0.1 and 0.4 and in particular between 0.2 and 0.3% by weight, based on the starting compounds, to achieve very good results.
  • the ratio between possibly modified hydrotalcite as a catalyst and co-catalysts can fluctuate in wide ranges, preferably the weight ratio is between 5: 1 to 1: 5, in particular between 3: 1 and 1: 3 and particularly preferably between 2: 1 and 1: 2.
  • the reaction of the compounds with active hydrogen atoms or the carboxylic acid ester with the alkylene oxides in a conventional manner at temperatures from 120 to 200 ° C, preferably 150 to 180 ° C and pressures of 1 to 5 bar.
  • the amount of alkylene oxide to be added is not critical and can be, for example, 1 to 100, preferably 2 to 50 and in particular 2 to 20 moles of alkylene oxide per mole of H-active compound or Amount of carboxylic acid esters.
  • Ethylene oxide, propylene oxide and / or butylene oxide can be used as alkylene oxides, preferably ethylene oxide.
  • Both inorganic and organic acids can be added as acids.
  • inorganic acids are particularly suitable mineral acids such as sulfuric acid, hydrochloric acid and / or phosphoric acid.
  • Both the so-called fatty acids can be used as organic acids 6 to 22 carbon atoms as well as lower carboxylic acids with 1 to 4 carbon atoms (only the carbon atoms of the hydrocarbon structure are counted, not the carbon atoms of the Carboxyl groups), which can optionally be additionally modified with hydroxyl groups.
  • the lower carboxylic acids such as lactic acid and acetic acid are preferred as organic acids and / or citric acid.
  • the acids are in the form of aqueous solutions, preferably 10 to 90% by weight Solutions added.
  • the acids are at least in equimolar amounts, based on Hydrotalcite and possibly existing co-catalysts - used.
  • the specific amount added Acids are of course dependent on the acid strength.
  • molar amounts are recommended on acids to hydrotalcite and possibly co-catalysts from 1: 1 to 4: 1.
  • the addition of the acids at temperatures above the melting point of the alkoxylated nonionic surfactants occur at temperatures between 70 and 95 ° C. This will be practical best carried out so that the reaction mixture obtained after the alkoxylation maintains at these temperatures and adds the acid.
  • the addition of acid ensures that the hydrotalcite decomposes.
  • the decomposition products of hydrotalcite prove to be water-soluble and do not lead to clouding or sedimentation of the alkoxylated nonionic surfactants. Accordingly, it is possible to use the method according to the invention elaborate filtration of any modified hydrotalcite.
  • the acid treatment according to the invention is a workup of the water-soluble ones Connect decomposition products of hydrotalcite, for example by separating the aqueous phase from the organic phase.
  • the alkoxylated nonionic surfactants obtained by the processes according to the invention can be used without further filtration. No precipitation occurs even after prolonged storage or sedimentation on them are therefore suitable as a nonionic surfactant for the production of Washing, rinsing and cleaning agents and for the production of cleaning cosmetics, especially of liquid products such as liquid textile detergents, hair shampoos and like.
  • the calcined hydrotalcite was dissolved after stirring for 10 minutes. It became one in the Melt clear reaction mixture obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Animal Behavior & Ethology (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Detergent Compositions (AREA)
EP00910696A 1999-03-03 2000-02-24 Verfahren zur herstellung alkoxylierter nichtionischer tenside Expired - Lifetime EP1156994B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19909272A DE19909272A1 (de) 1999-03-03 1999-03-03 Verfahren zur Herstellung alkoxylierter nichtionischer Tenside
DE19909272 1999-03-03
PCT/EP2000/001502 WO2000051955A1 (de) 1999-03-03 2000-02-24 Verfahren zur herstellung alkoxylierter nichtionischer tenside

Publications (2)

Publication Number Publication Date
EP1156994A1 EP1156994A1 (de) 2001-11-28
EP1156994B1 true EP1156994B1 (de) 2004-04-14

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EP00910696A Expired - Lifetime EP1156994B1 (de) 1999-03-03 2000-02-24 Verfahren zur herstellung alkoxylierter nichtionischer tenside

Country Status (5)

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US (1) US6646145B1 (enExample)
EP (1) EP1156994B1 (enExample)
JP (1) JP4780835B2 (enExample)
DE (2) DE19909272A1 (enExample)
WO (1) WO2000051955A1 (enExample)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10161350A1 (de) * 2001-12-13 2003-06-26 Cognis Deutschland Gmbh Verfahren zur Herstellung alkoxylierter Verbindungen
US7923425B2 (en) * 2006-08-21 2011-04-12 Henkel Ag & Co. Kgaa Low-foaming, acidic low-temperature cleaner and process for cleaning surfaces
DE102006041904A1 (de) * 2006-09-07 2008-03-27 Cognis Ip Management Gmbh Verfahren zur Herstellung von Alkylenoxidanlagerungsprodukten
DE102006041903A1 (de) * 2006-09-07 2008-03-27 Cognis Ip Management Gmbh Verfahren zur Herstellung von Alkylenoxidanlagerungsprodukten
US20080167501A1 (en) 2007-01-08 2008-07-10 Bayer Materialscience Llc. High productivity alkoxylation processes
JP5358835B2 (ja) * 2009-05-12 2013-12-04 ライオン株式会社 副生成物の少ない脂肪酸ポリオキシアルキレンアルキルエーテルの製造方法
EP2319802A1 (de) 2009-11-10 2011-05-11 Cognis IP Management GmbH Mischmetalloxyde und deren Verwendung als Katalysatoren für die Alkoxylierung
MY188147A (en) * 2014-04-24 2021-11-24 Lion Corp Method for producing fatty acid alkyl ester alkoxylate
CN109627431B (zh) * 2018-12-06 2022-03-15 上海多纶化工有限公司 脂肪酸甲酯聚氧乙烯醚的生产方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3833076A1 (de) 1987-09-29 1989-04-06 Lion Corp Alkoxylierungskatalysator
DE3843713A1 (de) 1988-04-25 1989-11-02 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
ES2050178T3 (es) 1988-04-28 1994-05-16 Matsushita Electric Industrial Co Ltd Sistema de altavoz.
DE4010606A1 (de) 1990-04-02 1991-10-10 Henkel Kgaa Verwendung von hydrophobierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
WO1992012951A1 (de) 1991-01-22 1992-08-06 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
DE4101740A1 (de) 1991-01-22 1992-07-23 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
TW397686B (en) * 1993-08-11 2000-07-11 Takeda Chemical Industries Ltd Antacid compositions and pharmaceutical compositions
JP2940852B2 (ja) 1993-12-24 1999-08-25 ライオン株式会社 脂肪酸ポリオキシアルキレンアルキルエーテルの製造方法
DE19611999C1 (de) * 1996-03-27 1997-07-17 Henkel Kgaa Verfahren zur Herstellung alkoxylierter Fettsäurealkylester

Also Published As

Publication number Publication date
JP4780835B2 (ja) 2011-09-28
EP1156994A1 (de) 2001-11-28
WO2000051955A1 (de) 2000-09-08
JP2003519086A (ja) 2003-06-17
DE50006070D1 (de) 2004-05-19
US6646145B1 (en) 2003-11-11
DE19909272A1 (de) 2000-09-07

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